Polyhydroxy amino ethers and acylation products thereof



3,929,265 POLYHYDROXY AMINO ETHERS AND AtCYLA- TION PRODUCTS THEREOFJohn D. Zech, Wilmington, DeL, assignor to Atlas (l'hemical industries,Ind, Wilmington, Del, a corporation of Delaware No Drawing. Filed Apr.23, 1957, Ser. No. 654,442 16 Claims. (Cl. 260-'-4M.5)

This invention relates to processes for the synthesis of nitrogencompounds derived from polyhydric alcohols having at least threehydroxylgroups per molecule and to products which may be produced by suchprocesses. Particularly, it relates to acylation products of suchnitrogen compounds which are surface-active agents.

An object of this invention is to provide a new class of polyhydroxyprimary and secondary amino ethers which are useful intermediates forthe chemical synthesis of amides, esters, ester amides, substitutedpolyhydroxy amino ethers, and quaternary ammonium compounds.

An additional object of this invention is to provide a new class ofsurfactants which are acylation products of fatty acids and polyhydroxyamino ethers.

A further object of this invention is to provide aclass of surfactantswhich form stable emulsions over a wide temperature range.

It is also an object of this invention to provide a class of compoundswhich, when used as additives in jet fuels, impart anti-staticproperties thereto.

The above objects of this invention, as well as additional objects, willbe apparent to those skilled in the art from a consideration of thefollowing description.

Briefly summarized, methods of the present invention involve thefollowing steps:

ammonia or an amine of the type describedbelow.

(3) The product of step 2, which ;is in the form of a hydrohalide, isneutralized with an alkali .to liberate a polyhydric amino ether.

(4) From these ethers, which are chemical intermediates, amides andester amides as well as other reaction products can be derived.Surface-active agents can be synthesized by reacting the ethers with analiphatic monocarboxylic acid, in the manner described below.

The initial step of the synthesis is the condensation of a polyhydricalcohol having three or more hydroxyl groups per molecule withepichlorohydrin or its equivalent in the presence of a catalyst. Thereaction can be exemplified by the following chemical equation:

[o-GEdonornOrh In the above equation x is a number of three or more andn is a number from one to x. R is an hydroxyl-free radical of apolyhydric alcohol. When the polyhydric alcohol is a hexitol, from oneto about three mols of epichlorohydrin are usually preferred.

Thereaction illustrated above may be performed in the presence of anacidic catalyst as is well known in the prior art. Preferred catalystsare those of-the Lewis acid type which include, for example, BF B1etherate, AlCl SnCl but H 50 p-toluene sulfonic acid and the like mayalso be used.

The reaction may be carried out at any temperature from about 75 to 175C., the preferred range being p r. 3,029,265 IC Patented Apr. 10, 1962from to C. A temperature of 90 usually insures a reasonable reactionspeed. Above'about 130, decomposition and dehydration of hexitols oftentends to occur.

While the reaction is generally carried out in the absence of solvent ordiluent, such materials maybe used if desired to lower the viscosity, asan aid in controlling temperature, or to permit the use of lowertemperatures where high melting polyhydric alcohols (such as hexitols)are used.

Suitable polyhydric alcohols or mixtures thereof for use in thisconnection include, among others, triols (such as glycerol), tetritols(such as erythritol), pentitols (such as xylitol, arabitol, etc), thehexitols (such as sorbitol, mannitol, dulcitol, etc.), polyhydricalcohols containing more than six hydroxy groups and polyhydric alcoholssuch as for example pentaerythritol, trimethylolethane, andtrimethylolpropane which are polymethylol alkanes.

Suitable polyhydric alcohols also include anhydro derivatives of otherpolyhydric alcohols (having at least three hydroxy groups per molecule)in which water has been removed from two hydroxyl groups to form acyclic ether, such as 1,4 sorbitan, and also external ethers ofpolyhydric alcohols, as, for example diglycerol.

Another group of suitable polyhydroxy alcohols comprises themonosaccharides such as sorbose, mannose, glucose, arabinose and xyloseas well as methyl glucoside and similar compounds.

The polyhydric alcohols useful in this invention include those, of thetype listed above, which have been modified by etherification withalkylene oxides such as ethylene oxide, 1,2 propylene oxide and mixturesthereof. As is well known in the .art, such a reaction yields productscontaining polyoxyalkylene chains of varying length. If a mixture ofalkylene oxides is employed, a given polyoxyalkylene chain may containboth the oxyethylene group and the oxypropylene groups. For the purposeof utilization in this invention the most suitable polyoxyalkyleneethers of polyhydric alcohols are those formed by reacting from one tosix mols of alkylene oxide with each mol of polyhydric alcohol. The termpolyhydric alcohol when used hereafter is intended to include all of theabove exemplified compounds and mixturesthereof.

In lieu of epichlorohydrin other reactive epihalohydrins may be usedsuch as epibromohydrin and epiiodohydrin. Other compounds such asl-chloro-2,3 epoxybutane and 2-chloro-3,4 epoxybutane are also suitablefor the condensation.

The reaction products are for the most part very viscous syrups. Theyare complex mixtures which may contain residual free polyhydric alcoholin addition to various isomeric epichlorohydrin-polyhydric alcoholcondensates (also referred to as chlorhydroxypropyl ethers).

The following are a few specific examples of the initial reaction whichare intended to illustrate the process but not to limit it to thespecific reactants involved.

EXAMPLE I.-1

613 grams of anhydrous sorbitol were heated to a reaction temperature ofbetween 97 and 107 C.; 1.5 cc. of BF, (45% BF etherate catalyst werethen added.

Thereafter, 389 grams (molal ratio 1:1.25) of epichlorohydrin were addeddropwise, over a period of 34 minutes with vigorous stirring and controlof cooling, so as to maintain the temperature within a specified'limit.The temperature was maintained for one hour between 97 and 107 C. by theaddition of heat to insure completion of the reaction.

Additional examples are given in Table I. In each case, the procedurefollowed was similar to the procedure outlined above. However, the molalratio of polyhydric alcohol to epichlorohydrin was varied, as was theepichlorohydrin addition time, the reaction temperature and the amountof catalysts used.

4 120 C., with an optimum range from about 30 C. to about 100 C. Thisreaction is exothermic and it may be carried out in an inert solvent,such as water or a Table I Grams Molal Co. of Reaction Example Alcoholused Grams epiehlororatio 45% BF temp Epichloro-hydrin Total reactionNo. alcohol hydrin alcohol: etherate C. addn. time time epl.

I-l Sorbitol 613 389 1:1. 25 1. 5 1 hr 34 mm I-2 do 1, 200 1, 220 1:2 3.2 hrs. 20 mm I8- d0 729 925 1:2. 2.0 2 hrs. min. I4 ErythritoL- 122 92.51:1 0.5 1 hr. min. I-5- SorbitoL- 1, 459 925 1:1. 3.0 3 hrs. I-6- do 651578 1:1. 75 1. 5 1 hr. 45 min. I7 -d0- 1, 184 602 1:1 8.0 1 hr. 38 min.I8.. do-- 1, 200 1, 220 1:2 3.0 2 hrs. 7 min. I- do-- 712 361 1:1 1. 5 2hrs. 0 min. I-lO- do 600 610 1:2 1. 5 D0. I-lld0 1, 200 1, 220 1:2 3.0 3hrs. 40 min. I-12- do 913 1,040 1:2. 25 2.0 2 hrs. 0 min. I-13- -dO 913578 1:1. 25 2.0 1 hr. min. I-14- .(10 2,123 1, 345 1 :1. 25 5. 0 2 hrs.0 min 146. do 1, 184 3, 160 1:5. 25 1 3. 4 5 hrs. 30 min. 146...GlyceroL- 460 463 1:1 1.0 1 hr. 40 min. I-17--- d0- 460 698 1:1. 5 1. 251 hr. 53 min. I-18 Dl-glycerol 166. 5 92. 5 1:1 1. 0 1 hr. 37 min. I-19Ttimethylol-ethane--- 170 131 1:1 2.0 1 hr. 31 min.

1 Grams.

2 Prepared in 250 cc. dloxane. After reaction was complete, 14 g.trimethylolethane crystallized out and were filtered oil.

Considering now the production of surface-active compositions which givestable emulsions over a wide range of temperatures, their synthesisinvolves the reaction of the condensation product of the initial stepwith armmonia, a reactive primary amine or a polyamine. The reactionwith ammonia or a reactive primary amine may be illustrated by theequation set forth below.

The reaction product, which is in the form of a hydrochloride, isneutralized in the next step with an alkali to liberate a polyhydricprimary or secondary amino ether. This reaction may be illustrated asfollows:

(3) OH H01 [00 zOHCH NHR/ln [OCHflJHOHzNHRh R +nNeCl+nHiO \(OH) x-n Thesymbols in the equations above have the same meaning as Equation 1. Inaddition, each R is independently selected from the group consisting ofhydrogen, alkyl, hydroxy alkyl, cyclo alkyl, and polyhydroxy alkyl. 7The reaction takes place between ammonia or a reactive primary aliphaticamine (primary amines having the amino group attached to tertiary carbonatoms, because of steric hindrance effects, will not react with theproducts of step 1 to give products which are suitable for thesubsequent reaction and the term reactive amine, when used henceforth,is intended to exclude such amines) and the product of the first stepsynthesis. It is carried out in the presence of an excess of ammonia orreactive primary amine. The presence of the excess reactant serves tosuppress polycondensation.

Preferred reaction temperatures range from 20 to about lower alcohol. Itis also possible to use an excess of the primary amine as a solventwhere the primary amine being used in a liquid. In the case of ammoniaor a volatile primary amine, such as methyl or ethyl amine, it isdesirable to carry out the reaction under pressure so as to avoid theloss of the volatile reactant and thereby maintain it in excess of thetheoretical molecular requirements.

By carrying out the reaction under super atmospheric pressure, highertemperatures can be used and the reaction time correspondingly reduced.

Suitable primary mono-amines for use in this connection are exemplifiedby methyl amine, ethyl amine, n-propyl-amine, isopropyl amine, n-butylamine, sec. butyl amine, isobutyl amine, n-amyl amine, n-hexyl amine,cyclo-hexyl amine, ethanol amine, propanol amine, and 1-amino-2, 3dihydroxy propane (glycerol amine) or mixtures thereof.

Mixtures of primary amines, such as hexadecyl, octadecyl, octadecenyl,and octadecadienyl may also be used. Such products are sold by Armourand Company under the generic trade name Armeen. These products are morefully described on page 62 of the 1953 edition of Handbook of MaterialTrade Names by Zimmerman and Levine.

It is desirable, in many cases, to use the lower primary amines, whichare sufl'iciently low-boiling, so that they can be readily separated bydistillation from the reaction products which are non-volatile.

Suitable amines also include polyamines which contain not more than 3amino nitrogen atoms. Such amines are exemplified by the ethylenepolyamines and the propylene polyamines and include ethylene diamine,diethylene triarnine, propylene diamine, dipropylene triamine,triethylene triamine (N-aminoethyl piperazine), hydroxyethyl diethylenetriamine (and other reaction products of lower alkylene oxides such asethylene oxide, propylene oxide or mixtures thereof with polyamines,provided however, that the resulting oxyalkylated amine contains atleast two amino hydrogens), 3, 3' iminobis propylamine and mixtures ofthe above.

The neutralized reaction product of the polyamine derivative whichcorresponds to the monoamine product of Equation 3 may be represented bythe following formula wherein all symbols have their previous meaning:

and wherein each is independently selected from the group of monovalentradicals consisting of:

an autoclave, the flask was rinsed with 110 grams of water, and therinse water Was also added to the auto clave. The temperature of theautoclaves' contents was 2;; raised to 120 C. during a /2 hour period,and thereafter Y 2y Y 2 held at 120 C. for 1.5 hours while the pressuredevel- (c) H NE oped was 8085 p.s.i.g.

The autoclaves contents were discharged, the autoclave rinsed with 700g. of water and the combined Y Y solution was heated to 100 C. to boiloff much of the /C2H4 excess NH Thereafter, 840 g. of 50% NaOH solu-NAJZHPNE, tion (5% excess) were added and the reaction mixture 02114 washeated to 110 C. to distill olf additional ammonia and water. Theresulting syrup amounted to 4,230 grams (2) and contained 10 moles ofcombined epichlorohydrin -NE-O2H4N NE residues. The amino-ether syrupwhich was thus pre- CIH pared contained approximately 0.7 equiv. ofnitrogen wherein further, in each radical, y is either 2 or 3; and perequlv. of eplchlorohydrm' each E is independently selected from thegroup consist- EXAMPLE II-Z g of y g and y lower y PTOVidsd'hOW- 308grams of the condensation product of Example ever that at least one E ishydrogen. I-l were combined with 1160 cc. of a 40% solution of Thereaction with ammonia or primary amine produces methyl amine at roomtemperature and the mixture a hydrochloride of an amino ether. The aminoth r is was allowed to stand over night. The temperature graduliberatedby the addition of an amount of alkali equivaally rose for several hoursto about 35 to 40 C. and lent to the chlorine content of theepichlorohydrin conthen gradually decreased. After standing over night,densate used. The excess ammonia or primary amine, the reaction mixturewas heated on a steam bath for as the case y is then pped oif and can bereseveral hours to insure completion of the reaction. Since cycled tothe next batch. methyl amine is a relatively volatile amine, some of theThe alkali used must be strong enough to liberate the excess boiled oifduring this heating. amino ether from the amino hydrochloride and suit-The reaction mixture was then treated with an amount able alkalis areexemplified by the hydroxides of the of aqueous NaOH equivalent to thechlorine content of alkali metals. the epichlorohydrin condensate used.The excess amine The amino rs can be separated from the by-prodandsolvent were stripped off, using vacuum at the end uct alkali metalchloride by known methods, such as of the stripping operation.Thereupon, the product was dilution with a non-solvent for the chloridef ll w d by taken up in sufiicient methanol to obtain a suitablefilterfiltration and ion exchange- In some cases, he p ing viscosity andthe crystalline NaCl was filtered on. ence of the chloride is notobjectionable and the prod- The methanol was then stripped ofi", leavingthe polynot can be used without separating it. hydroxy amino ether as aresidue which still contained The following are a few specific examplesof the foro di chloride. mation of polyhydroxy amino ethers and are tobe con- The reaction yielded 325 grams of polyhydric amino sidefedillustrative Y- is t0 be noted that every ether which contained 4.86%nitrogen by weight. Addinitrogen compound used meets the fundamentalrequiretional Examples II-3 to -I I-23 follow in Table II.

Table II Condensate Grams Amount Product Percent Example No. of Exampleconden- Amine used of yield, N

No. sate amine g.

Butyl amine--. 1,100 cc-- 539. 5 Ethanolamine 2,000 cc. 863 40% methylamine- 1,000 co 213. 5 NH4OH (28% N113)- 40% methyl amine" Glycerylamine Butyl amine- Gyclohexyl amine Armeen SD l 1,000 e0 345 5. 9 70000-..... 373 8. 71 Diethylene triamine 900 cc- 365 12. Hydroxy ethylethylene diamine.. 105 g 357 7. 8v

1 A soft fatty amine sold by Armour dz 00. under this designation.

ment of containing at least two hydrogen atoms bonded to basic nitrogen.

EXAMPLE II-l To a flask containing 2,645 grams of a condensate preparedby a procedure similar to that of Example I-5, which contained 10 molesof combined epichlorohydrin, was added 2,430 grams of 28% aqueousammonia (40 moles, 300% excess). The addition of the ammonia -took.placeat temperatures from 15 to 26 C. and extended over a half hour. Thesolution was charged to 75 some esterification results. Since-the ammoethercontains free hydroxyl groups in the portion of the moleculederived from alcohol, and since further, it may contain additional freehydroxy groups if the primary amine used in the second step was analkanol amine (such as, for instance, ethanol amine or propanol amine),there is always ester formation. Thus, the final reaction product is acombined amide and ester. The relative extent of amidation andesterification may be varied by varying the amount of fatty acid reactedwith the polyhydroxy amino ether.

Amidation of the polyhydroxy amino ethers may be either total orpartial. If only one amino nitrogen atom capable of amidation is presentin the ether molecule, such as would be the case when the ether isformed by the seriatim reaction of one molecule of polyol, one moleculeof epichlorohydn'n and one molecule of a reactive primary monoamine,then the surface-active compositions of this invention are totalamidation products. However, when more than one molecule ofepichlorohydrin attaches to a given polyol molecule and/or when apolyamine is used to form the amino ether then a molecule of the ethermay contain a plurality of amino nitrogen atoms which are capable ofamidation. In the case of such poly-amino ethers it is essential that atleast one amino nitrogen be amidated. How many more will be amidated isa function of the carboxyhamino nitrogen ratio of reactants. While someesterification always occurs, lower ratios favor products which arepredominantly amides whereas ratios above 1:1 tend to favor increasedester formation. Generally any ratio of carboxylztotal nitrogen from0.75 to 6 may be used, those compounds prepared using ratios of from 3to 6 having higher ester content. However, the range from 0.75 to 2.0 isgenerally preferred.

Total amidation of an ether derived from a primary mono-amine can beillustrated by the following equation:

x is a number of at least 3 and n is a number from 1 to x.

"C-is the acyl radical of an aliphatic monocarboxylic acid.

R is an hydroxyl-free radical of a polyhydric alcohol.

R is hydrogen, alkyl, cyclo alkyl, hydroxy alkyl or polyhydroxy alkyl.

Each R is independently selected from the group consisting of hydrogenatoms and acyl radicals of aliphatic monocarboxylic acid.

Each A is independently selected from the group consisting of hydrogen,alkyl, cyclo alkyl, hydroxy alkyl, polyhydroxy alkyl, acylated hydroxyalkyl, and acylated polyhydroxy alkyl.

In the case of the polyamines which have previously been described, thecorresponding amidation products may be represented as having theformula:

wherein common symbols have the same meaning as in Equation 4 above and,wherein each X is independently 8 selected from the group of monovalentradicals consisting of:

wherein, further, y is an integer from 2 to 3, and eachY isindependently selected from the group consisting of hydrogen, acylradicals of aliphatic monocarboxylic acids, hydroxy lower alkyl andacylated hydroxy lower alkyl, provided however that at least one Y isthe acyl radical of an aliphatic monocarboxylic acid.

The amidation reaction, in which at least one mol of H 0 is evolved permol of acid reacted, is carried out at an elevated temperature, withinthe range of about and about 220 C.

If none, or only part of the salt, was removed prior to this reaction,it can be filtered off from the amide either with or without dilutionwith a non-solvent for the salt. For some applications, the salt may beallowed to remain in the final product.

As has been stated, it is also possible to only partially amidate anamino ether which has been made from a polyolepihalohydrin derivativewherein the ratio of epihalohydrin to polyol was greater than 1:1. Thus,the amidation products formed by reacting a monocarboxylic acid with theether made from a polyol-epihalohydrin derivative and ammonia or areactive primary mono-amine may be generally represented by thefollowing formula:

O-CHz-OHO R-OHN A n R[OCH:CHO R-CH:-NHA] (O R) X- mn wherein x is anumber of at least 3; n is a number from 1 to x;

And m is a number from zero to the quantity x--n; and wherein further,

0 II RIIC is the acyl radical of an aliphatic monocarboxylic acid;

R is an hydroxyl-free radical of a polyhydric alcohol;

Each A is independently selected from the group consisting of hydrogen,alkyl, cyclo alkyl, hydroxy lower alkyl, polyhydroxy lower alkyl,acylated hydroxy lower alkyl and acylated polyhydroxy lower alkyl; and

Each R is independently selected from the group consisting of hydrogenatoms and acyl radicals of aliphatic monocarboxylic acids.

The corresponding generalized formula for products formed from polyaminederivatives is as follows:

( [0 --c Hz-CHO R'-CH-a-X]n R-[OCH2CHOR"'-CHg-Z]m (O R') xmi-n) whereinZ has the meaning assigned in Formula 3-A, X has the meaning assigned inFormula 4-A and x, m, n,, R and R'" have the same meaning as in Formula5.

In the case where total amidation does not occur and consequently onlypart of the amino groups are reacted, the resulting amides will containfree amino groups and can, therefore, be used as cationic surfactants,whereas the fully amidated products are non-ionic surfactants.

contained 1.046 equivalents of combined epichlorohydrin residues) wasadded 925 grams (3.19 moles) of oleic acid derived from tall oil. Thereactant molal ratio of fatty acid to nitrogen was approximately 4.421.The

Suitable mono-carboxylic acids for the amidation inreaction was allowedto proceed for 4 hours at 200 C., clude the higher fatty acids such aslauric, myristic, pa'lmiafter which time the Acid Number of the amideproduct tic, stearic, oleic, linoleic, linolenic, ricinoleic, 12-hydroxywas 29; and thereafter for an additional hour at 230 C., stearic acid,erucic, as well as mixed acids such as the fatty at which time the AcidNumber of the amide product was acids derived from animal and vegetablefats and oils, 17. ;To this product were added .346 equivalent of NaOHtall oil, naphthenic acids and acids obtained by the oxidaand thereaction continued for another hour at 230 C. tion of petroleumfractions. While fatty acids having The final product, which wascalculated to contain 10.8% 12 to 18 carbon atoms are preferred for thisreaction, it soap, had an Acid Number of 11. is also possible to use ashort chain acid such as acetic X Q N acid, provided that the aminoother which is being amid- PLE HI ated has a long alkyl chain which wasderived from a A11 addlhoflal P Q 0f the ammo-ether p g 111 fatty aminein the previous synthesis step. hp Was PPQ 10 i e r AS i well known i hul i h b h a (which contained .848 equlvalent of combinedepichlorohydrophobe and a hydrophile function. .In the present hyqfln hh Was added grams moles) 0f compounds, the hydrophobe function ca b ib td oleic acid derived from tall 011. The react-ant molal ratio by eitherthe carbon chains derived from the amine or 20 0f fafty acid t0 hltfogehWas approximately The those d i d f o f tty id, or b h h reaction wasallowed to proceed for 4 hours at 200 C., short chain acid as, forexample, acetic is employed, a after Whlch tlme the Acld Nlllhbel: theamlde Product long chain amine hould be used In gengral it is pre. WaSand thereafter for an addltlonal hour at 230 0., ferred that thecombined carbon chain lengths of amine at which time Acid Number of theamide Pf and fatty acid groups used in the preparation of the sur- T0thls prochlct added equlvalent f t t fthj i ti t t l 12 of NaOH and thereact1on continued for another hour The following are examples of theamidation reaction: at 9 'y l cl lg fk g li f a alclllated t0 EXAMPLE1H4 .contaln 1 .1 0 soap, 2 an 01 um er 0 1-8.

A portion of the amino-ether prepared in Example M III-4 II-l wasstripped to 183 C. To this ether (which con- 310 grams of 01616 301dWfife added 286 grams of tained 1.44 equivalents of combinedepichlorohydrin resithe product of Example II-1 (molal ratio carboxylzN,dues) was added 856 grams (2.95 moles) of oleic a id 1.1 :1). The mixlngtook place at between 70 and.100 0. derived from tall oil (sold as thetrademarked product Thereafter, the reactants were heated to thereaction tem- Acintol FA-Z). The reactant molal ratio of fatty acidperature of between 6 and n l there f r to nitrogen was approximately29:1. The reaction Was a period of three hours and 20 m1nutes. allowedto proceed for 4 hours at 200 (3., after which Imt1alv1scos1ty was highdue to the format on of amine time the Acid Number of the amide productwas 11.5; oaps. H as the mp a was ralsed and t and thereafter wasallowed to proceed for an additional amidat-lon proceeded, the v1scos1tydecreased. hour at 230 0., at which time the Acid Number of the 40 Thresultant product has an acld number of a final amide product was 6.7.saponification number of 51 and an OH number of 40.

Additional Examples LII-5 to III-33 are presented in EXAMPLE 1H4 TableIII. In each instance, the reaction procedures were Another portion ofthe amino-ether prepared in 'Examsimilar to those in Example III-4 whichwas described ple 11- 1 was stripped to 180 C. To this ether (whichabove in narrative form.

Table III Amine ether Characteristics Example Grams synthesized GramsMol ratio Reaction Product No. Acid used acid in Example ethercarb0xyl:N Reaction time tcmp., 0. acid N0. number Sap. OH

number number One use of the amides synthesized in the manner describedis as the emulsifier in a water-in-oil emulsion drilling fluid. Typicaldrilling fluids employing the amide as the emulsifier also include awater phase (preferably containing salt), and an oil phase.

A water-in-oil emulsion drilling fluid was prepared using the product ofExample III-4. The drilling fluid had the following formulation:

The above formulation is representative of many which can be prepared.All of them exhibit remarkable stability even under high temperatureconditions.

Some of the products of the present invention are useful as corrosioninhibitors, particularly for brine solutions containing hydrogen sulfidewhich are commonly encountered in the oil industry. For example, theproduct of Example III-16, when tested for corrosion inhibitingproperties in accordance with the procedure described in detail in TheDevelopment of a Standard Laboratory Procedure for Screening CorrosionInhibitors for Use in Oil and Gas Wells by E. C. Greco and J. C.Spalding (paper prepared for National Association of CorrosionEngineers, 1954), gives excellent corrosion protection (95.4%protection) when used at a concentration of 100 ppm. in a brine solutioncontaining 500 ppm. of hydrogen sulfide.

The products of the invention are also useful for creating water-in-oilemulsions for a number of other uses. One applicaiton relates to marinediesel engines which employ oil as a circulating lubricant. In order tomaintain lubricating properties, it is desirable that any water whichmay get into the lubricating system be incorporated in the lubricant inthe form of a temperature-stable emulsion, rather than being present asa separate phase. The following formulation is illustrative of the widerange of utility afforded by the instant emulsifiers for suchapplications.

If the emulsifier of Example III6 is added to lubricating oil in theratio of three parts by weight of emulsifier to 70 parts by weight oflubricating oil, it will then be possible to incorporate amounts ofwater ranging from 0 to 150 parts. Throughout the entire range ahomogeneous water-in oil emulsion will exist. The emulsion can be formedwhether the water is salt water, such as is commonly found in marineservice, or fresh water, which might result from engine exhaust. Theseemulsions are stable over a wide range of temperatures.

Compositions of this invention find additional utility as anti-staticadditives to hydrocarbon fuels of the low vapor pressure wide cutgasoline type. Fuels of this type may usually be characterized as havinga Reid vapor pressure within the range of about 2.0 to 3.0. Handlingthem has, in the past, presented a considerable explosion hazard becausetheir vapor pressure at ambient temperatures is high enough that when abody of fuel is maintained in an ordinary vented tank the amount ofvapor is sufficient to provide an explosive mixture but insufiicient tolower the proportion of air to such a degree that the mixture above thefuel is not explosive. Consequently fuels of this sort have beensusceptible to ignition by sparks such as can be generated by staticelectricity build up in the fuel body.

It has been found that compounds of this invention have the property oflowering the electrical resistivity of the fuels and/or inhibiting thebuildup of static electricity in them. In this way the explosion hazardin handling the fuel is greatly minimized when added to such fuel insmall quantities of about 0.2% and less. Preferred compositions of theinvention for this purpose are those which are soluble in the fuelwithout haze at concentrations up to 0.2% by weight at temperatures aslow as 60 F. The amount of composition of the invention added foranti-static use should be suflicient to reduce the electricalresistivity of the fuel to a value below about 1 10 ohm-centimeters.Usually that amount will be between about 0.2% and 0.0025%.

A fuel which is particularly susceptible to this static electricalexplosive hazard and in which the compositions of the present inventionare particularly useful as antistatic additives is that used for jetengines and referred to as JP-4 fuel. It is completely described inmilitary specification MIL-F-S 624C.

In Table IV, are listed a number of examples of additive content of jetfuels containing compounds of the invention. Each of these fuels wasprepared by simply adding the amount of additive listed in the table toJP-4 fuel. Each of the resulting fuels had a specific resistivity below1 X 10 ohm-centimeters and was useful as a fuel in jet engines. Testsperformed on each fuel indicated that it could be handled withoutbuildup of static electricity and that no precipitate haze appeared inthe fuel when it was cooled to a temperature of 60 F.

Many changes in processing details may be made without departing fromthe principles set forth herein and the invention is to be broadlyconstrued in accordance with the following claims.

What is claimed is:

1. A process comprising condensing sorbitol with epichlorohydrin in themolar ratio of 121.25, aminating the product of the aforesaid reactionwith ammonia at a temperature of about 20 to about C. in the presence ofan excess of ammonia, liberating the ether condensation product with analkali, and thereafter amidating and esterifying the resultingpolyhydroxy amino ether by contacting it with oleic acid at atemperature within the range of about to about 220 C.

2. A process comprising the steps of (1) aminating the condensationproduct of a polyhydric alcohol, having from 3 to 6 hydroxy groups permolecule, and an epihalohydrin, with a basic nitrogen-containingcompound selected from the group consisting of ammonia, reactive primaryalkyl monoamine, reactive primary hydroxy lower alkyl monoamine,reactive primary cyclo alkyl monoamine, reactive primary polyhydroxylower alkyl monomanie, and alkylene polyamines containing from 2 to 3amino nitrogen atoms and at least 2 amino hydrogen atoms per molecule;(2) liberating polyhydroxy amino ether condensation products byneutralizing the product of step 1 with an alkali; (3) and thereafteracylating the polyhydroxy amino ether condensation products of step 2 toform a fatty acid amide.

3. A process comprising the steps of (l) aminating the condensationproducts of sorbitol and epichlorohydrin with a basicnitrogen-containing compound selected from the group consisting ofammonia, reactive primary alkyl monoamine, reactive primary hydroxylower alkyl monoamine, reactive primary cyclo alkyl monoamine, reactiveprimary polyhydroxy lower alkyl monoamine, and lower alkylene polyaminescontaining from 2 to 3 amino nitrogen atoms and at least 2 aminohydrogen atoms per molecule; (2) liberating polyhydroxy amino ethercondensation products by neutralizing the product of step 1 with analkali; (3) and thereafter acylating the polyhydroXy amino ethercondensation products of step 2 to form a fatty acid amide.

4. The reaction product made by the process of claim 2.

5. The process of claim 4 wherein the acylation is carried out bycontacting the polyhydroxy amino ether condensation products with ahigher fatty acid which contains from 12 to 18 carbon atoms permolecule.

6. The process of claim 5 wherein said nitrogencontaining compound isammonia.

7. The process of claim 5 wherein said nitrogencontaining compound ismethylamine.

8. The process of claim 5 wherein said nitrogencontaiuing compound isethylene diamine.

9. The process of claim 5 wherein said nitrogencontaining compound isdiethylene triamine.

10. The reaction product made by the process of claim 3.

14 11. The reaction product made by the process of claim 5.

12. The reaction product made by the process of claim 6.

13. The reaction product made by the process of claim 7.

14. The reaction product made by the process of claim 8.

15. The reaction product made by the process of claim 9.

16. The reaction product made by the process of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS2,669,336 Schmidt et al Feb. 2, 1937 2,525,771 Cook et a1. Oct. 17, 19502,538,072 Zech Jan. 16, 1951 2,581,464 Zcch Jan. 8, 1952 2,539,199Morison Mar. 11, 1952 2,598,213 Blair May 27, 1952 2,609,370 Gaver et alept. 2, 1952 2,775,604 Zech Dec. 25, 1956 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No, 3,02%265 April 10 1962 John D. ZechIt is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Columns 9 and 10 Table III underthe heading "Reaction time", Example N0,III--30 for "3 hrs, 50 min." read 3 hrs. 0 min. column 1O lines 9 l7 and25 "equivalent" each occurrence read equivalents column 12 line 63 for"monomanie" read monoamine Signed and sealed this 11th day of December1962.

(SEAL) Attest:

ERNEST w. SWIDER DAVID LADD Attesting Officer Commissioner of Patents

3. A PROCESS COMPRISING THE STEPS OF (1) AMINATING THE CONDENSATION PRODUCTS OF SORBITOL AND EPICHLOROHYDRIN WITH A BASIC NITROGEN-CONTAINING COMPOUND SELECTED FROM THE GROUP CONSISTING OF AMMONIA, REACTIVE PRIMARY ALKYL MONOAMINE, REACTIVE PRIMARY HYDROXY LOWER ALKYL MONOAMINE, REACTIVE PRIMARY CYCLO ALKYL MONOAMINE, REACTIVE PRIMARY POLYHYDROXY LOWER ALKYL MONOAMINE, AND LOWER ALKYLENE POLYAMINES CONTAINING FROM 2 TO 3 AMINO NITROGEN ATOMS AND AT LEAST 2 AMINO HYDROGEN ATOMS PER MOLECULE; (2) LIBERATING POLYHYDROXY AMINO ETHER CONDENSATION PRODUCTS BY NEUTRALIZING THE PRODUCT OF STEP 1 WITH AN ALKALI; (3) AND THEREAFTER ACYLATING THE POLYHYDROXY AMINO ETHER CONDENSATION PRODUCTS OF STEP 2 TO FORM A FATTY ACID AMIDE. 